Amines } 13.1 Structure of Amines 13.7 Method of Preparation of Dlazonium ‘ 13.2 Classification Salts 13.3 Nomenclature 13.8 Physical Properties 13.4 Preparation of Amines 13,9 Chemical Reactions 13.5 Physical Properties 13.10 Importance of Diazonlum Salts In 13.6 Chemical Reactions ‘Synthesis of Aromatic Compounds Bi 2 Ga Ba BS 6 TSO Is IO Topic —> >» Maximum total weightage Is of Chemical > Maximum SA and LA | type questions were Reactions of Amines. asked from Chemical Reactions of Amines. > Maximum VSA type questions were asked from Chemical Reactions of Amines. QUICK RECAP AMINES © Amines : ‘These are alkyl or aryl derivatives of ammonia and are obtained by replacing one, two or three hydrogen atoms by alkyl/aryl groups. © scanned with OKEN Scanner© Nomendature: In common system, an aliphatic @)_Structur amine is named by prefixing alkyl group to sp'-hybridised and the geometry of amines is amine, i.e, alkylamine, In IUPAC system, amines are named as alkanamines, In secondary and tertiary amines, when two or more groups are the same, the prefix di or tri Eis C or H) is less than 109.5% is appended before the name of alkyl group. © Classification: : Nitrogen orbitals in amines are pyramidal. Due to the presence of unshared pair of electrons, the angle C—N—E, (where ‘Amines Aliphatic Arom —o—_— ry (1*) Amines Secondary (2*) Amines ‘Tertiary (3°) Amines -NH, group attached to. SNH group attached to DN group attached to thre aly groups (RN) slgraup(R— NH.) (wo alkyl groups (RNID) Simple Mixed Simple Mixed Both alkyl groups Both alkyl groups All threealkyl Either all three are different or are same (R)NH) are different groupsare same (wo are same, one is different (R'NHR) (RN) (R'RR'N of RRR'N) © Preparation: Reduction of nitro compounds: J RNO, — Seiler Fellic Gabriel phthalimide synthesis : orl/Pd or Lialllyether : CO 4 KOM.) (CL Sy i) RX, A ti cor ii) Hfor OHT/HJO/8 Hofmann's ammonolysis method: wit, IK NH, Mendius reduction: 41 yy1or tual ether RON ~NaligyGyHsOH Hofmann bromamide degradation : Bo _—_ RCONH Reduction of amides: KOH, & . LiAIFiylether RCONH, or NaCqiigOTT > Limitations of Gabriel phthalimide @ Physical properties : synthesis : — Ibis used for the preparation of only 1° amines. tert-Butylamine is a 1° amine, > but cannot be prepared by this method. In this case, elimination takes place. — Aromatic 1° amines cannot be prepared by this method because aryl halides do not undergo nucleophilic substitution in water due to hydrogen bonding between reaction with potassium phthalimide Nu, and H,0 molecules. under mild conditions. / > Lower amines are gases and liquids but higher amines are solids Primary and secondary amines have higher boiling points than other organic compounds due to hydrogen bonding. > Primary and secondary amines are soluble © scanned with OKEN Scanner© Chemical properties: > Basic character of amine: — Amines are basic in nature due to the presence of lone pair of electrons on nitrogen atom, — Aliphatic amines are stronger bases than ammonia due to +Z effect of alkyl groups Present in amines. — Aromatic amines are weaker bases than ammonia due to ~/effect of aryl group. ~ Beside inductive effect, there are other effects like steric effect, solvation effect, » Chemical reactions : RNH, <@ anuicr 2° amine > 1° amine >NH,. ~ In aqueous phase, despite of inductive effect, solvation effect and steric hindrance also play an important role. ‘Thus, the order of basicity of amines is (C,Hs),NH > (C,H,),N > C.H;NH, > NH; and (CH,),NH > CH;NH, > (CH,),N > NH, (RCO),0 [arcoce > RNHCOR’ CUCL yale. KON, ar TRE cio RNC (Carbylamine reaction) Quatemary KCl. -120 * (Unpleasent smell) sH3COCI ANH) & HNO. RNHCOC H<—SSop °—>ROH + Nj + H,0 Rod CeltsS0,01 RNHCOR'‘<—o STI RNHSO,C Hs (Hinherg's tes) (Soluble in NaOH1) / > _ Identification of primary, secondary and tertiary amines : y Test Primary amine Secondary amine Tertiary amine i 1. | Reaction with nitrous s alcohol with | Gives oily nitrosoamine | Formsnitrite in cold acid. effervescence of N, | which gives Lieberman's gas, which is soluble in waterand on heating gives nitrosoamine, nitrosoamine test. Reaction withbenzene sulphonyl chloride (Hinsberg’s reagent) Gives N-alkylbenzene- sulphonamide which is soluble in alka Gives N.N-dialkylbenzene sulphonamide which is insoluble in alkal No reaction 3. | Carbylamine test: | Forms carbylamine No reaction No reaction oil reaction : Reaction with CS, and HgCl,. isothiocyante with characteristic unpleasant smell of mustard oil. Reaction with | or isocyanide (RNC) chloroform and characteristic alcoholic KOH unpleasant odour, 4. | Hofmann’s mustard | Forms N-substituted | No reaction No reaction > Electrophilic substitution reactions of arylamines : Aniline undergoes electroph substitution reactions. NH) group is ortho- and para-directing and a powerful activating group. © scanned with OKEN ScannerNH NH, Br Br oo wn oS orgs $03H b ous Sulphate aed Arl ‘ Br, ATE [Ys arNSBE{-| (Balz-Schiemann reaction) NaNOn/Cu, ArCl cucinict 3 PAINO2 0 oe H,0 Sandmeyer) a ope ¢ Cubstise | farNgX}]}— > ArOH fetcttod Aen (CuCN/KCN NaNO, |_NaNO2 Arc] cwnia cxgo.a AINOn Gattermann) °F cat Cat a ls jomberg reaction meson) A os SOLS ArCN > — Reactions involving retention of diaze group (cot uupling reactions) : Ceti, OH/OH™ GALI AIN=NC,HNH2 g (1/5, 2020) LL. Carry out the following conversion: Benzoic acid to aniline. (1/5, AL 2019) 12, Write the chemical equation involved in the following reaction : Hofmann bromamide degradation reaction (AI 2019, 1/5, 2018, 1/2, AI 2016, 2012, 1/3, Foreign 2011) 13. State and illustrate the following : Gabriel synthesis (1/5, 2018, 1/2, AI 2013C, 1/3, Foreign 2011) 14. How do you convert the following : Ethanenitrile to ethanamine (1/3, AI 2015) 15. Write chemical equation for the following conversion : Benzyl chloride to 2-phenylethanamine. (173, Delhi 2012)| 16. Why cannot primary aromatic amines be prepared by Gabriel phthalimide synthesis? (1/2, AI 2011C) (2 marks) 17. How will you convert the following : (i) Nitrobenzene into aniline (ii) Ethanoic acid into methanamine (2/3, Delhi 2014) 18, How are the following conversions carried out? (i) CH,CH,Cl to CH,CH,CH,NH; (ii) Benzene to aniline (Delhi 2012C) 13.5 Physical Properties (1 mark) 19. Out of CH,NH, and CH,OH, which has higher boiling point? (2020) 20. Arrange the following compounds in decreasing order of their boiling points : Butanol, Butanamine, Butane (1/3, 2020) 21. Propanamine and N,N-dimethylmethanamine contain the same number of carbon atoms, © scanned with OKEN Scannereven though propanamine has higher boiling point than N,N-dimethylmethanamine. Why? (AI2019) 22. Give reasons for the following : Primary amines have higher boiling point than tertiary amines. (1/3, AI 2016, 2014, 2011) 23, Arrange the following in the increasing order of their boiling points : C.H:NH,, CH,OH, (CH,),N (1/5, Dethi 2015) 24, Arrange the following compounds in increasing order of solubility in water : G\H:NH,, (GoH;)sNH, C)H5NH, (Delhi 2014, AI 20110) 25, Outof CHjNH; and (CH3)N, which one has higher boiling point? (Delhi 2014C) 26. Account for the following : Ethylamine is soluble in water whereas aniline isnot. (1/3, Delhi 2014C, AI 2011) HE 02 marks) 27. Arrange the following compounds as directed : (i) Inincreasing order of solubility in water: (CH)),NH, CH,NH3, CHsNH, (ii) In increasing order of boiling point (C\Hy:NH, (C3H).N, GH;NH, (2/3, 2020) 13.6 Chemical Reactions (Amines) (1 mark) 28. Out of the following, the strongest base in aqueous solution is (a) methylamine (c)_ trimethylamine (d) aniline. (b) dimethylamine (2020) 29, CH,—NH, on heating with CHCl; and alcoholic KOH gives foul smell of @ €S-cuon (b) €S-cuxe 30. 31. 32, 33. 34, 35. 36. 37. 38. 39. 40. © €S-atex @ cua Arrange the following compounds as directed In decreasing order of basic strength in aqueous solution : (CH,),N, (CH,),NH, CH,NH, (1/3, 2020) Give the structures of A and B in the following sequence of reactions : Fe/H NaNO, +HCl NaNO, +HCl CoHsNO, AC, 4 SOB (2/3, 2020) Arrange the following in increasing order of base strength in gas phase. (CxH,)sN, C;HsNH,, (C)H5)NH (Delhi 2019) Carry out the following conversion: Bromomethane to ethanol. (1/5, AI 2019) Give reason: (CH,),NH is more basic than (CH,),N in an aqueous solution, (1/5, 2018) Arrange the following in the decreasing order of their basic strength in aqueous solutions : CH NH, (CH,).NH, (CH,),N and NH, (1/3, 2018C, Delhi 2012) Describe the following by giving the relevant chemical equation : Carbylamine reaction (1/3, 2018C, 1/2, AI 2012) Give a simple chemical test to distinguish between the following pair of compounds : (CH)),NH and (CH,)N_ (1/5, Delhi 2015) the following in increasing order of (2020) roaniline and p-toluidine (1/2, Al 2015, AE 2015C) Arrange the following in increasing order of basic strength : C.H;NH;, C,HsNHCH;, C,H;CH,NH, (1/2, Al 2015, Delhi 2014) How will you convert the following = Aniline into N-phenylethanamide (Write the chemical equations involved.) (1/3, Delhi 2014) © scanned with OKEN Scanner4. 43. 50. 51. ‘Arrange the following in increasing order of basic strength. C,H:NH,, G,H;NHCH,, C,H,N(CH,), (Delhi 2014) Which of the two is more basic and why? CH,NH, or NH, (Foreign 2014) Which of the two is more basic and why? NH NH, O-0 CH3 (Foreign 2014) Which of the two is more basic and why? NH, CH.NH, or (Foreign 2014) Arrange the following in increasing order of their basic strength in aqueous solution : CH,NH;, (CH)sN, (CH)):NH (Delhi 2013) Complete the following reaction equation : C,H.NH, + Bros) > (1/2, AI 2012) 7. Rearrange the following in an increasing order of their basic strengths : C,H.NH,, C,H,N(CH,);, (C.H,),NH and CH,NH; (AI2011) State reasons for the following : pK, value for aniline is more than that for ethylamine. (1/3, AT2011) How will you differentiate between aniline and ethylamine? (AI 2011) Why is an alkylamine more basic than ammonia? (Foreign 2011) How will you bring about the following conversion : Ethanamine to ethanoic acid (Delhi 2011C) (2 marks) 52. 53. How will you distinguish between the following pairs of compounds (i) Aniline and ethanamine (ii) Aniline and N-methylaniline (2/3, 2020) Distinguish between the following : (i) CH,CH,NH, and (CH,CH,),NH (i) Aniline and CH,NH, (2/5, 2020) Give reasons (i) Although NH, group is o/p directing in electrophilic substitution reactions, 55. 37. 58. 59. 61. yet aniline, on nitration gives good yield of m-nitroaniline. (ii) (CH,),NH is more basic than (CH,),N in an aqueous solution. (2/5, 2020) Write the structures of the main products of the following reactions : NH; - (ch,co,0 @ ~Fyridine Wi €S-s0, (2/5, 2018) . (a) Give a simple chemical test to distinguish between aniline and N,N-dimethylaniline, (b) Arrange the following in the increasing order of their pK, values C,HsNH;, C,H;NH,, CsHsNHCH, (2/5, 2018) Give reasons for the following : (i) Aniline does not undergo Friedel- Crafis reaction. (ii) (CH,),NH is more basic than (CH,),N in an aqueous solution. (2/3, A12016, 2014) How do you convert the following : (i) C.H,CONH, to C,H;NH, (ii) Aniline to phenol (2/3, AL 2015) Ilustrate the following reactions giving suitable example in each case : (i) Ammonolysis (ii) Acetylation of amines (2/5, Foreign 2015) Give the structures of A, B and C in the following reactions : (i) GHNO, SHUI, 4 NNO, p 2K WO ¢ (i) CHyCN 22" 4 S45 g Be, KOH, (, (2/3, Delhi, A 2014) Account for the following (i) Aniline does not give Friedel-Crafts reaction. (ii). pK, of methylamine is less than that of (2/3, Delhi 2014C) © scanned with OKEN Scanner62. (i) 63, 65. 67. Arrange the following compounds in an increasing order of basic strength : C\HiNH3, CyHsN(CH,)s. (CH,):NH and CH,NH, (ii) Arrange the following compounds in a decreasing order of pK, values GHsNH;, CsHsNHCHs, (C,Hs),NH and C,H;NH; (Delhi 20140) Complete the following reactions = (i) CH\CH,NH, + CHCl; + ale. KOH —> NH (i) + HChiaq) —> (2/3, AL 2013) Write the main products of the following reaction: Br, ¢ NOH (i) CHy-C—-NH, 2 § (2/3, Al 2013) Give chemical tests to distinguish between the following pairs of compounds (i) Aniline and ethylamine (ii) Ethylamine and dimethylamine (Delhi 2013C) Give reasons: i) Aniline isa weaker base than cyclohexyl amine, (ii) Its dificult to prepare pure amines by ammonolysis of alkyl halides. (AI2013C) Give reasons: (i) Electrophilic substitution in aromatic amines takes place more readily than benzene (ii) CH,CONH, is weaker base than CH,CH,NH,. (AI2013C) How would you account for the following : (Aniline is a weaker base than cyclohexylamine. (ii) Methylamine in aqueous medium gives reddish-brown precipitate with FeCl, (A12012C) (3 marks) 69. (a) Write the chemical reaction of methyl amine with benzoyl chloride and write the IUPAC name of the product obtained (b) Arrange the following in the increasing order of their pK, values : CH;NH;, NHy CH;NH;, (C;H,);NH (3/5, 2020) Give one chemical test to distinguish between the compounds of the following pairs: (i) CH.NH, and (CH,),NH (ii) Aniline and ethanamine (b)_ Why aniline does not undergo Friedel- Crafts reaction? (A12019) 71. Give reasons : (i) Acetylation of aniline reduces its activation effect. (ii) CHNH, is more basic than C,H;NH,. (iii) Although —NH, is ofp directing group, yet aniline on nitration gives a significant amount of m-nitroaniline. (Delhi 2017) 72. Write the structures of A, B and C in the following : (i) CeHs—CONH,, 70. (a) Brylag. KOH 4 KI_ NaNO, +HCl a c B osc KCN, LAI, (i) cHy-c1 S254 SY 5 CHCL, + ale, KOH a (Delhi 2016) 73. Write the structures of main products when aniline reacts with the following reagents : (i) Bry water (i) HCL (iii) (CHyCO),O/pyridine (3/5, Delhi 2015) 74, Write the chemical equations involved when aniline is treated with the following reagents : (Br, water (ii) CHCl, + KOH (iii) HCL (Al2015) 75. Write the structures of A, B and C in the following reactions: ' Sn+HGl, | NaNO. + HCI (i) Catigno, 8S g§ SOE Sg eal > c © scanned with OKEN ScannerKON, | _Lialliy HNO, (i) CHI Ss A$ 8 oc (3/5, Foreis 76. An aromatic compound ‘A’ on treatment with, aqueousammoniaand heating formscompound ‘B which on heating with Br, and KOH forms a compound °C of molecular formula CH.N. Write the structures and IUPAC names of compounds A, Band C. (Dethi 2015C) 77. Give the structures of products A, Band Cin the following reactions : KON, , WAI, | tHNOs () CHCH Bro 4 Sg Sc B Hcl, « Ale Nao Cc (Delhi 2014, 2013) 13.9 Chemical Reactions (Diazonium salts) (1 mark) 78. Write the structures of A and B in the following reactions : CHAN ICH SNL 4 HOMYS g (4/5, 2020) 79. Carry out the following conversion: /pritrotoluene to 2-bromabenzoic acid (1/5, AT 2019) 80. Write the structure of the main product of the following reaction : NCI cu,ct,on - Tl (1/5, 2018) 81. Complete the following reaction equation : C,H;N,CI + H,PO, + H;0 —> (Delhi 2015C, Al 2013, 2012) 82. The conversion of primary amines into diazonium salts is known as ae (A12014) 83. Complete the following reaction : mL #0 GHC! Rime? (0/3, A12013) 84, State and illustrate the following : Coupling reaction (1/2, AI 2013C, Foreign 2011) 6 , MOH Br, Gi) cHt,coon > 4 SR, aromatic 85. How is the following conversion carried out : Aniline to p-hydroxyazobenzene. (1/2, Delhi 20120) 86. How will you bring about the following conversion : Nitrobenzene to phenol (1/2, Delhi 2011C) 87. How will you bring about the following conversion : Aniline to chlorobenzene ‘Write the chemical equation involved. (1/2, Delhi 2011C) 88. How will you bring about the following conversion : Aniline to benzonitrile, (2marks) 89. (a) Write the reaction involved in the following: Diazotisation (b)_ Give reason : Aromatic diazonium salts are more stable than aliphatic diazonium salts. (2/5, 2018) 90, Write chemical equations for the following conversions : (i) Nitrobenzene to benzoic acid. (ii) Aniline to benzyl alcohol. (2/3, Delhi 2012) 91. Illustrate the following with an example of reaction in each case (i) Sandmeyer reaction (ii) Coupling reaction. (AI 2012C, Delhi 2011C) (Dethi 2011C) (3 marks) 92. Write the structures of main products when benzene diazonium chloride reacts with the following reagents : (i) CuCN (ii) CH,CH,OH (ai) KI (Dethi 2019) 93. Write the structures of compounds A, B and Cin the following reactions : (a) CH—cooH 844, 4 AekOHe, pLlich sale KOH, © scanned with OKEN Scanner(Ox/Cu oA CHsCOCUpyridine p£tscocurn (0) CHANSBE) ae Cc (Al 2017) 94. Give the structure of A, B and C in the following reactions : (0) cqrgn ser 2% 4 HAMS p NL NavOpsU, 4 mK nom] Cc (Dethi 2013) (ii) CgtHgNO, SESS 4 (5 marks) 98. An aromatic compound ‘A’ of molecular formula C,H;ON undergoes a series of reactionsasshown below. Write thestructures of A,B, C, Dand Zin the following reactions: Br, + KOH c CH;CH,OH B aah CeHsNHy . CHCl, | fbn EB D (Delhi 2015) Write the structures of main products when benzenediazonium chloride (CHNJCI) reacts with the following reagents (a) HBE/A (b) Cu/HBr Gi) Write the structures of A, Band Cin the following reactions : (a) gH NO, SESS 4. 96. (i) NaNO, + HCL CN, , Liallly HNO; () cH, S854 5 SS (Foreign 2015) H,CH,C L 7 N-CHy H,CH,C~ TUPAC name: N-Ethyl-N-methylethanamine cl NO}, NO, 2, 4-Dinitrochlorobenzene N-Methylpropan-2-amine (2° amine) N—CH,CH, HC? [N,N-Dirnethylethanamine 5. 2,4, 6-Tribromoaniline 6. CH,CH,NHCH, CH; NH, z 2-Aminotoluene 8. (a) But-3-en-2-amine (b) N-Phenylethanamide 9. The ammonolysis of alkyl halides with ammonia isa nucleophilic substitution reaction in which ammonia acts as a nucleophile by donating the electron pair on nitrogen atom to form primary amine as the initial product, Now, the primary amine can act as a nucleophile and combine with alkyl halide (if available) to give secondary amine and the reaction continues in the same way to form tertiary amine and finally quaternary ammonium sall, Thus, a mixture of products is formed and it is not possible to separate individual amines from the mixture. NU os CH,COOH — >> CH,CONH, "> CH,NH,, «@ oO) © scanned with OKEN ScannerlL. COOH oO Nip — Benvoicacid Ammonium Benzamide benzoate NH, O 1, KOH Aniline coonH, ALOya =I CONH, 12, R-CONH, + Br; +4NaOH —> Acid amide R—NH, + Na,CO, + 2NaBr + 2H,0 13. Gabriel phthalimide synthesis : In reactionphthalimideisconvertedintoits potassium salt by treating it with alcoholic potassium hydroxide. Then potassium phthalimide is heated with an alkyl halide to yield an N-alkylpthalimide which is hydrolysed to phthalic acid and primary amine by alkaline hydrolysis CON LOW oxi lewst NaOH grant OS} NCH, Tiyan cots ‘COOH Cx + GH NH, COOH — Ethylamine forme 14, CH,CN +4(H] 32292809), cH .cH.NH, Ethanenitile thanamine CHCl CH-CN —CHy—CH,-NHy 15. © 5) ust) Beni cherie 16. Primary aromatic amines cannot be prepared by Gabriel’ phthalimide synthesis because aryl halides do not undergo nucleophilic substitution with the anion formed by phthalimide. 2-Phenylethanamine 17. (i) NO, NH, + 6[H] Tei, oO +2H,0 Nitobantme Aine oO ‘i PC, il (ii) CHyCOOH —*> CHy—C—Cl Ethanoic acid Hy (Acetic acid) O° BryKOU I CHy-NH, <—cH,—C— NH, Methanamine 18, (i) cH,cH,cI 2s. cH,cH,c Chloroethane Propane nitrile CHCH,CHNIY i, 1-Propanamine No, O (i) Cys Oo (OJ Benzene Nitrobenzene Ani NH, ny Fete 19. CH,OH has higher boiling point than CH,NH,. ‘The hydrogen bonding in alcohols is stronger than that of amines because oxygen is more electronegative than nitrogen, 20. Decreasing order of boiling points of given compounds: Butanol > butanamine > butane 21. Primary amines (R - NH) have two hydrogen atoms on nitrogen which can undergo intermolecular hydrogen bonding whereas no such hydrogen bonding is present in tertiary amines (R,N). So, primary amines boil at a higher temperature than tertiary amines. 22. Refer to answer 21. 23. Increasing order of boiling points : (CH,),N < C,H,NH, < C;H,OH ‘Tertiary amine does not have hydrogen to form hydrogen bonding and hydrogen bonding in alcohol is stronger than that of primary amines because oxygen is more electronegative than nitrogen. 24. C,HsNH, < (C,H,);NH < C,H;NH, 1° amines are more soluble in water than 2° amines. Aniline due to large hydrophobic benzene ring is least soluble. 28. Refer to answer 21. 26. Ethylamine is soluble in water due to formation of intermolecular hydrogen bonds with water molecules. However, in aniline due to large © scanned with OKEN Scannerhydrophobic aryl group the extent of hydrogen bonding decreases considerably and hence aniline is insoluble in water. 27. (i) CH;NH; < (CH)):NH < CHNH, 1° amines are more soluble in water than 2° amines, Aniline due to large hydrophobic benzene ring is least soluble. (Gi) 1° amines have two, 2° amines have one while 3° amines have no hydrogen linked to nitrogen. The degree of association due to hydrogen bonding and hence the boiling point increase as (C.H,),N < (C,Hs)2NH < C;HsNH, 28, (b) : The order of basicity of the given compounds is (CH,),NH > CHNH, > (CH,)sN > CH.NH.. ‘There is a subtle interplay of the inductive effect, solvation effect and steric hindrance of alkyl groups which decides the basic strength of alkyl amines in the aqueous state. 29, (b) : Primary amines when warmed with chloroform and alcoholic solution of KOH produce isocyanides or carbylamines which have foul smell. 30. In case of small alkyl groups like —CH, the order of basicity is secondary amine > primary amine > tertiary amine due to solvation effect and +1 effect of —CH; group. (CH,),NH > CH,NH, > (CH)N pk, 327 338 422 31. CHyNOHSS CH.NH, (a) NaNO} + HCl osc 32. GH,NH, < (C)Hs):NH < (CH-)sN Ni/H, cH,—Br HENS CH, — CN > Bromomethane HNO, CH,CH,NH, ——*> CH,CH,OH Ethanol C.HSN3Cl @® 33. 34, In aqueous solution, 2%amine is more basic than 3°amine due to the combination of inductive effect, solvation effect and steric hindrance. 38. (CH,);NH > CH.NH, > (CH,),N > NH, 36. Carbylamine reaction is the reaction in which 1° amines produce a bad smelling compound when treated with chloroform in the presence of, alkali, RNH, + CHCl, + 3KOH (alc. —> RN = C+ 3KCl+ 3H,0 Itis the test for primary amines. 37. Whentreated with benzenesulphonyl chloride (Hinsberg’s reagent), (CH,),NH forms insoluble N,N-dialkylbenzene sulphonamide which is insoluble in KOH whereas tertiary amine does not reactaat all. NH, b NH, NO, CH; p-nitroanilive p-toluidine Electron withdrawing group (-NO;) on benzene ring decreases the basicity and electron donating group (-CH,) on benzene ring increases the basicity of compound. 39, CHsNH, < C,H;NHCH, < C,H,CH,NH, C,HeNH; and CJHsNHCH, are less basic than aliphatic amine C,HsCH;NH, due to lone pair of nitrogen is in conjugation with benzene ring. But due to +1 effect of —CH, group in C,H.NHCHs, itis more basic than CH NH, I NH H-N—C—CH, 40. ICHOIO,, Pyridine Aniline N-Phenylethanamide (acetanilide) 41. Increasing order of basic strength in gaseous te is as follows : sNH, < CgHsNHCH) < C,H,N(CH,)» Asthe number of CH, groups (effect) attached to nitrogen increases, its basicity will increase. 42, Methyl amine is more basic than ammonia because of the presence of electron donating methyl group (+F effect), which increases the electron density on nitrogen atom 43. CH4(C,H,) NH, is more basic than C,H-NH, due to electron releasing nature of methyl group which pushes electrons towards nitrogen. 44, CH,NH; is more basic than C,H;NH) because in aniline the lone pair of electrons on nitrogen are involved in resonance. 45. In case of small alkyl groups like —CH, the order of basicity is secondary amine > primary © scanned with OKEN Scanner= amine > tertiary amine due to solvation effect and +L effect of CH, group. (CH),N < CHNH, < (CH);NH NH, Br Br 46. CoHIsNHy+ Brgy —> +3HBr Br 47. (CoH;):NH < CsHsNH; < CsHSN(CH;)2 -Nu, (NaNoymtel . CHy 2 Gp noarsmeR? CHSCHs 51. CHACHNIL typo arsavee? CHDCHOH. E6071, Cy COOH 52. (i) Refer to answer 49. (ii) Aniline gives carbylamine test, ie, on treatment with ale. KOH and chloroform followed by heating it gives offensive odour of phenylisocyanide but N-methylaniline being secondary amine, does not show this test, 53. (i) When heated with an alcoholic solution of KOH and CHCl, ethylamine gives foul smelling ethyl isocyanide. Diethylamine does not give this test. (ii) Aniline gives white or brown precipitate with, bromine water, NH, NH, (white ppt.) Methylamine does not react with bromine water. 54. (i) Nitration is carried out with conc. HNOy in the presence of cone. H,SO,, In the presence of these acids, the -NH, group of aniline gets protonated and is converted into -NH, group. This positively charged group acts as a strong electron withdrawing and meta-directing group. Hence, the incoming electrophile goes to m-position, (ii) In aqueous solution, 2°amine is more basic than 3amine due to the combination of inductive effect, solvation effect and steric reasons. 55. (i) Refer to answer 40. ca i) (Sa song? Het i or Benzene sulphoryt chloride ° Wes S—NC § Scu, N.Nedimethytbenzene sulphonamide 56. (a) Aniline undergoes isocyanide test (carbylamine reaction) whereas, N, N- dimethylaniline does not. NH, Oo + CHCl, + 3KOH—4> Aniline Ne +3KCL+ 3H, Phenyl iocyanide (foul smell) (b) Stronger the base, lower will be the pk, value. C)HSNH, < CHsNHCH; < CH;NH; pK, 3.29 4.63 9.38 57. (i) In Friedel — Crafis reaction, AICI, is added asa catalyst which is a Lewis acid. ft forms a salt with aniline due to which the nitrogen of aniline acquires positive charge. This positively charged nitrogen acts as a strong deactivating group, hence aniline does not undergo Friedel — Crafts reaction. Nu, +00,» ©) (ii) Refer to answer 34. CONH, py, NH, 58. (i) er 2 Be, + KOH or Lb Benzamide Aniline © scanned with OKEN Scannerc a > Nic on 10 = +N + HCL Phenol 59. (i) Ammonolysis : Alkyl halides when treated with ethanolic solution of ammonia give a mixture of primary, secondary, tertiary amines and quaternary ammonium salt. (ys R225 eH, a XN Primary” Secondary [Rx RANK AX RN Quaternary Tet ammoniam lt "Sine (ii) Acetylation of amines : ‘The process of I introducing an acetyl group (CH;—C—) into a molecule is called acetylation. 9 Il CH3CH,NH, + CH;—C—cl > 9° I CH;—C—NHG)H; + HCl N-Ethyl acetamide 60. (i) C.H;NO, +#“> C.H.NH, a CH,08 22 cHNicr c 2 (i) cH,cn 2S. cx,coon—cu,conn, a 8 By KOH, cy.NH, oa NaNO, + HCL TK 61. (i) Refer to answer 57(i). (ii) Inaniline, the lone pair of electrons of N-atom are delocalised over the benzene ring. As a result, electron density on the nitrogen decreases. In contrast, in CH;—NH;, +7 effect of CH, group increases the electron density on the N-atom. ‘Therefore, aniline is a weaker base than methylamine and hence, its pK, value is higher than that of methylamine. 62, (i) Increasing order of basic strength is C,H;NH, CH;NHCH,> C;HsNH, > (CyH,)NH 63. (i) CHy-CH,—NH; + CHCl, + 3KOH —> CH,—CH,-NC + 3KCI + 3H,0 (i) Sn, +H ee> &- Sucre 64. (i) Refer to answer 46. (ii) CH,CONH, CH,—NH, Methanamine 65. (i) Aniline gives white or brown precipitate with bromine water. NH) NH, Br Br +3Br,—> + 3HBr Br (white ppt Ethylamine does not react with bromine water. (ii), When heated with an alcoholic solution of KOH and CHCl, ethylamine gives foul smelling ethyl isocyanide, Dimethylamine does not give this test. 66. (i) Aniline is weaker base than cyclohexylamine because of resonance. Due to electromeric effect, the lone pair on nitrogen is attracted by benzene ring. Hence, donor tendency of —NH, group decreases, There is no resonance in cyclohexylamine. Electron repelling nature of cyclohexyl group further increases the donor property of NH, group. So, cyclohexylamine is a stronger base. Aniline {lesonance stuctues) Qehentlamine (No resonance) (ii) Refer to answer 9. 67. (i) Benzene ring in aromatic amines is highly activated due to the displacement of lone pair of nitrogen towards the ring, It results, increase in the electron density on the ring. This facilitates the electrophilic attack on the ring. (ii) In CH,CONH,, the lone pair of electrons on nitrogen. atom is involved in resonance with the © scanned with OKEN Scannercarbonyl group. So, the electron pair of nitrogen is not easily available for protonation. Hence, CH,CONH, is a weaker base than CH\CH,NH,. @ v on tA. cn, 68. (i) Refer to answer 66(). (ii) Methylamine forms hydroxide ions when dissolved in water due to the following acid - base equilibrium. CH,—NH, +H, These OH" ions react with Fe** ions to form ferric hydroxide, 2Fe + (OH —> 2Fe(OH), 69, (a) CHNH, + CHsCOCI—> 9 IL CH,NH—C—C,H, N-Methbenzami (b) Stronger the base, lower will be its pX, value. Hence increasing order of pK, values is, (C.H).NH < C,H3NH, < NH, < CHsNHy 70. (a) (i) Methylamine gives carbylamine test, ie, on treatment with ale. KOH and chloroform, followed by heating it gives offensive odour of methyl isocyanide. Dimethylamine does not give this test. (ii). Refer to answer 49, (b) Refer to answer 57 (i). 71. (i) After acetylation of aniline, acetanilide is formed in which due to the presence of 0 —tcn, group having -/effect,clectron density oon N-atom decreases and hence, activation effect of aniline gets reduced. ii) Refer to answer 44. (ili) Refer to answer 54(), 72. CONH, NH, o sy osc ag. KOH SROs a cl ay 1 Niko kL (c) (B) KCN. LiAlH, CH, > cH,CN >» CH,CH.NH, w @ CHCI, + ale. KOH CH;CH,NC cosas o 73. (i) Refer to answer 46. (ii) Refer to answer 63(ii). (iii) Refer to answer 40. 74. (i) Refer to answer 46, NH, (ii) +CHCL; + 3KOH—> Ailing 4+3KCl + 31,0 Phenyl iocyanide (iii) Refer to answer 63(ii). 75. (i) Refer to answer 60(3). (i) cH cHcn 2S cHycHyH, A a CH,CH,OH <0 | c BK 76. Formula of the compound °C indicates it is an amine. Since it is obtained by the reaction, of Br, and KOH with the compound ‘B’ so compound ‘s can be an amide, As ‘B" is obtained. from compound ‘A’ by reaction with ammonia followed by heating so, compound ‘A’ could be an aromatic acid. Formula of compound ‘C’ shows it to be aniline, then'B' is benzamide and compound ‘A’ is benzoic acid. ‘The sequence of reactions can be written as follows : COOH CONH, NH, OOO x B € UAL, (i) CH,CH,Br ®>.cH,cH,CN ~~] a cncn,cu.on <23&-cu,cn,cn, 1, oO ’ @ Iie, + NaOH (i) cH,coon SE CHCONH, CH,NC CgHCN Benzonitrile #07" (ay CH;COOH Renzoic acid @ cH, cH, Br ~O Bry o Sn/HCl NO, 7 CH, ete Noy, or “a4 Tank NH, Nicr cooH od Br Br KMno, eq Reduction, 80. CsHsN3CI + CH;OH Benzenediazonium chloride Cob + CHsCHO + Np + HCI Benzene Ethanal 81. C.H.N,Cl+ H,PO, + HO —> CyHy +N; + HyPO, + HCI 82. Diazotisation reaction. Nici OH 83. Yr + Ho —> +N) +HCl Phenol 84. Diazonium salts react with aromatic amines in weakly acidic medium and phenols in weakly alkaline medium to form coloured compounds called azo dyes by coupling at p-position of amines or phenols. Or 1+ HX{O)-o8 Phenol (us- 10] >» 278K, OH P Hydroxyszobenzene (Orange dye) 85. HNO, eo NH, ye? N= Nc Benzenediazonium chloride +(Op-ou Phenol wows tl -zneon _prHydroxyazobenzene (orange dye) NH NaNO, + HCL 23- 78K + ofr] SHS Benzenediazonium chloride Nycr NaNO, + HCI | “Tse” CuCN/Pyridine kN) CN Aniline Benzonitrile 89. (a) Diazotisation : ©- Nie NaNoye2tic1 222K Aniline Or N= NCi+ NaCl + 2H,0 Diazonium salt (b) Diazonium salts carry a nitrogen atom with 4 positive charge. This positive charge is well dispersed in aromatic diazonium salts through resonance as shown below : © scanned with OKEN ScannerSuch a charge delocalisation is not possible in aliphatic diazonium salts and hence they are less stable than aromatic diazonium salts NH, N3cr No, 90. (i) © 22, (6) z Nitrobenzene Aniline Mena alcohol 91. (i) Sandmeyer reaction : By this reaction nucleophiles like Cl, Br, CN> etc, can easily be introduced in the benzene ring by treating the diazonium salt solution with corresponding halogen acid in the presence of Cu(I) ion. Opmer Cu,Cly/HCL (Oya Benzenediazonium Chiorobenzene chloride (ii) Refer to answer 84, Njcr CN ~O=O Benzonitrile (ii) Refer to answer 80. N3cr I «© = © lodobenzene 93. (a) Refer to answer 77 (ii). (b) CcHyNsBE, SENOMCY , C,H.NO, A Nitrobenzene (a) pac G,H;NHCOCH, S229 CNH, Acetanilide Prridine Aniline © (3) 94. (i) Cok Nici PS + cH eN: ante Hom" Nu C,H_CONH, <>-C,H,COOH Senzamide Benzo acid © (ii) Refer to answer 60(i) CONH; NE, BryIKOH, NaNO, + HCL % 273K A CHCl | Nic NaOH, ern NC }———— I N3clr ¥ F 96. (i) (a) Oo ae o} Benzenediazonium —__Fluorobenzene Br (v) cube Benzenediazonium —_‘Bromobenzene chloride (ii) (a) Refer to answer 60(i). (b) Refer to answer 75(ii). <44@>>> © scanned with OKEN Scanner